New polymer and polymer light-emitting device using the same

ABSTRACT

Provided is a polymer comprising a repeating unit represented by formula (1),  
                 
 
wherein, A 1  represents a divalent group in which the bond distance ratio (bond distance of C(α)-A 1 /bond distance of C(α)-C(β)) is 1.10 or more; R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , each independently represent a hydrogen atom, alkyl group, alkyloxy group, aryloxy group, arylalkyloxy group, etc. The polymer is useful as a light-emitting material, a charge transporting material, etc.

This is a continuation of application Ser. No. 10/954,223 filed Oct. 1,2004, which is a continuation of application Ser. No. 10/309,101 filedDec. 4, 2002, now abandoned. The entire disclosures of both applicationSer. Nos. 10/954,223 and 10/309,101 are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a new polymer, a process for producingthe same, a polymeric fluorescent substance thereof, and a polymerlight-emitting device (hereinafter, may be referred to as “polymer LED”)using the same.

2. Description of the Related Art

High molecular weight light-emitting materials and high molecular weightcharge transporting materials are variously studied since they aresoluble in solvents, unlike low molecular weight materials, and can beformed into light emitting layers or charge transporting layers bycoating method. As the example, polyfluorene derivatives are known.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a new polymer whichcan be used as a light-emitting material, a charge transportingmaterial, etc., a process for producing the same, and a polymerlight-emitting device using said polymer.

That is, the present invention relates to a polymer having a polystyrenereduced number average molecular weight of 10³-10⁸, and comprising arepeating unit represented by the below formula (I),

wherein, A¹ is a divalent group represented by -Z- or -Z-Z- in which Zis an atomic group which may have a substituent; A¹ represents adivalent group in which the bond distance ratio (bond distanceC2-A¹/bond distance C2-C1) is 1.10 or more, in which C2 is the carbon ofa position, and C1 is the carbon of 6 position, respectively to A¹; R¹,R², R³, R⁴, R⁵, and R⁶, each independently represent a hydrogen atom, ahalogen atom, an alkyl group, alkenyl group, alkynyl group, alkyloxygroup, alkylthio group, an alkylamino group, aryl group, aryloxy group,arylthio group, arylamino group, arylalkyl group, arylalkyloxy group,aryl alkylthio group, arylalkylamino group, substituted silyl group,acyl group, acyloxy group, imino group, amide group, arylalkenyl group,arylalkynyl group, monovalent heterocyclic group, or cyano group; R² andR³ may be connected to form a ring; and R⁴ and R⁵ may be connected toform a ring.

DETAILED DESCRIPTION OF THE INVENTION

In the above formula, as the atom contained in Z, a hetero atom ispreferable, and as the hetero atom, Si, P, S, Ge, Sn, Se and Te areexemplified.

Examples of the atomic group Z having substituent are as follows.

In the formula, R each independently represents a hydrogen atom, ahalogen atom, an alkyl group, alkyloxy group, alkylthio group,alkylamino group, aryl group, aryloxy group, arylthio group, arylaminogroup, arylalkyl group, arylalkyloxy group, arylalkylthio group,arylalkylamino group, substituted silyl group, acyl group, acyloxygroup, imino group, amide group, arylalkenyl group, arylalkynyl group,monovalent heterocyclic group, or cyano group.

The bond-distance ratio in the above formula (I) is computable byoptimizing the molecular structure of a compound using quantum-chemistrycalculation. As the quantum-chemistry calculation method, semi-empiricaland non-empirical molecular orbital methods, and a density functionalmethod, etc. can be used. For example, by a density functional methodincluded in quantum-chemistry calculation program Gaussian 98, astructure-optimizing calculation of a compound can be performed using6-31 g* as a basis function, and b31yp as a density functionalapproximation, and the bond-distance ratio can be determined. (Ref: J.Chem. Phys., 98, 5648 (1993)).

The bond distance C2-A¹ is the distance from C2 to the atom of the groupA¹ to which C2 is directly bonded. When the repeating unit of formula(I) is asymmetrical, both bond distance ratios are 1.10 or more.

R¹, R², R³, R⁴, R¹ and R⁶ in the above formula (I) each independentlyrepresent a hydrogen atom, a halogen atom, an alkyl group, alkenylgroup, alkynyl group, alkyloxy group, alkylthio group, alkylamino group,aryl group, aryloxy group, arylthio group, arylamino group, arylalkylgroup, arylalkyloxy group, arylalkylthio group, arylalkylamino group,substituted silyl group, acyl group, acyloxy group, imino group, amidegroup, arylalkenyl group, arylalkynyl group, monovalent heterocyclicgroup, or cyano group. R² and R³ may be connected to form a ring; and R⁴and R⁵ may be connected to form a ring.

Preferably, R² and R⁵ are each independently alkyloxy group, alkylthiogroup, alkylamino group, aryloxy group, arylthio group, arylamino group,arylalkyloxy group, arylalkylthio group, or arylalkylamino group amongthem, and more preferably, alkyloxy group, aryloxy group, orarylalkyloxy group.

As the halogen atom, exemplified are fluorine, chlorine, bromine, andiodine.

The alkyl group may be any of linear, branched or cyclic, and usuallyhas about 1 to 20 carbon atoms, and the group may have a substituent.Specifically, exemplified are: a methyl group, ethyl group, propylgroup, i-propyl group, butyl, i-butyl, t-butyl, pentyl group, hexylgroup, cyclohexyl group, heptyl group, octyl group, 2-ethyl hexyl group,nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group,trifluoromethyl group, pentafluoroethyl group, perfluorobutyl, perfluorohexyl group, perfluorooctyl group, etc.; and preferably pentyl group,hexyl group, octyl group, 2-ethylhexyl group, decyl group, and3,7-dimethyloctyl group.

The alkenyl group may be any of linear, branched or cyclic, and usuallyhas about 2 to 20 carbon atoms, and the group may have a substituent.Specifically, exemplified are: ethenyl group, propenyl group, 2-propenylgroup, 1-methyl propenyl group, 2-methylpropenyl group, 1,2-dimethylpropenyl group, butenyl group, 2-methylbutenyl group, 1,3-butadienylgroup, pentenyl group, hexenyl group, cyclohexenyl group, heptenylgroup, octenyl group, 2-ethyl hexenyl group, trifluoroethenyl group,perfluorobutenyl group, perfluorohexenyl group, perfluorooctenyl group,etc.

The alkynyl group may be any of linear, branched or cyclic, and usuallyhas about 2 to 20 carbon atoms, and the group may have a substituent.Specifically, exemplified are: ethynyl group, propynyl group, 2-propynylgroup, 2-methyl propynyl group, butynyl group, 2-methylbutynyl group,1,3-butanediyl group, pentynyl group, hexynyl group, cyclohexynyl group,heptynyl group, octynyl group, 2-ethyl hexynyl group, fluoroethynylgroup, perfluorobutynyl group, perfluorohexynyl group, perfluorooctynylgroup, ete.

The alkyloxy group may be any of linear, branched or cyclic, and usuallyhas about 1 to 20 carbon atoms, and the group may have a substituent.Specifically, exemplified are: methoxy group, ethoxy group, propyloxygroup, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group,pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group,octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group,3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group,pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group,perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group,etc.; and preferably pentyloxy group, hexyloxy group, octyloxy group,2-ethylhexyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group.

The alkylthio group may be any of linear, branched or cyclic, andusually has about 1 to 20 carbon atoms, and the group may have asubstituent. Specifically, exemplified are: methylthio group, ethylthiogroup, propylthio group, and i-propylthio group, butylthio group,i-butylthio group, t-butylthio group, pentylthio group, hexylthio group,cyclo hexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthiogroup, laurylthio group, trifluoro methylthio group, etc.; andpreferably pentylthio group, hexylthio group, octylthio group,2-ethylhexylthio group, decylthio group, and 3,7-dimethyloctylthiogroup.

The alkylthio group may be any of linear, branched or cyclic, andusually has about 1 to 40 carbon atoms, and the group may bemonoalkylamino group or dialkylamino group. Specifically, exemplifiedare: methylamino group, dimethyl amino group, ethylamino group,diethylamino group, propyl amino group, dipropylamino group,i-propylamino group, diisopropyl amino group, butylamino group,i-butylamino group, t-butylamino group, pentylamino group, hexylaminogroup, cyclohexylamino group, heptylamino group, octyl amino group,2-ethylhexylamino group, nonylamino group, decylamino group,3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group,dicyclopentylamino group, cyclohexylamino group, dicyclohexylaminogroup, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group,etc.; and preferably pentylamino group, hexylamino group, octyl aminogroup, 2-ethylhexylamino group, decylamino group, and3,7-dimethyloctylamino group.

The aryl group may have a substituent, and usually has about 6 to 60carbon atoms. Specifically, exemplified are: phenyl group, C₁-C₁₂alkoxyphenyl group (C₁-C₁₂ shows 1-12 carbon atoms), C₁-C₁₂ alkylphenylgroup, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group,etc., and preferably C₁-C₁₂ alkoxyphenyl group, and C₁-C₁₂ alkylphenylgroup.

The aryloxy group may have a substituent on the aromatic ring, andusually has about 6 to 60 carbon atoms. Specifically, exemplified are:phenoxy group, C₁-C₁₂ alkoxyphenoxy group, C₁-C₁₂ alkylphenoxy group,1-naphtyloxy group, 2-naphtyloxy group, pentafluorophenyloxy group,pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazyloxygroup, triazinyloxy group, etc.; and preferably C₁-C₁₂ alkoxyphenoxygroup, and C₁-C₁₂ alkyl phenoxy group.

The arylthio group may have a substituent on the aromatic ring, andusually has about 6 to 60 carbon atoms. Specifically, exemplified are:phenylthio group, C₁-C₁₂ alkoxyphenylthio group, C₁-C₁₂ alkylphenylthiogroup, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group,pyrimidylthio group, pyrazylthio group, triazinylthio group etc.; andpreferably C₁-C₁₂ alkoxyphenylthio group, and C₁-C₁₂ alkylphenylthio.

The arylamino group may have a substituent on the aromatic ring, andusually has about 6 to 60 carbon atoms. Specifically, exemplified are:phenylamino group, diphenyl amino group, C₁-C₁₂ alkoxyphenylamino group,di(C₁-C₁₂ alkoxyphenyl)amino group, di(C₁-C₁₂ alkylphenyl)amino group,1-naphtylamino group, 2-naphtylamino group, pentafluorophenylaminogroup, pyridylamino group, pyridazinylamino group, pyrimidylamino group,pyrazylamino group, triazinylamino group etc.; and preferably C₁-C₁₂alkylphenylamino group, and di(C₁-C₁₂ alkylphenyl)amino group.

The arylalkyl group may have a substituent, and usually has about 7 to60 carbon atoms. Specifically, exemplified are: phenyl-C₁-C₁₂ alkylgroup, C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂alkyl group, 1-naphtyl-C₁-C₁₂ alkyl group, 2-naphtyl-C₁-C₁₂ alkyl group,etc., and preferably C₁-C₁₂ alkoxyphenyl-C₁-C₁₂ alkyl group, and C₁-C₁₂alkylphenyl-C₁-C₁₂ alkyl group.

The arylalkyloxy group may have a substituent, and usually has about 7to 60 carbon atoms. Specifically, exemplified are: phenyl-C₁-C₁₂alkyloxy group, C₁-C₁₂ alkyloxy phenyl-C₁-C₁₂ alkyloxy group, C₁-C₁₂alkylphenyl-C₁-C₁₂ alkyloxy group, 1-naphtyl-C₁-C₁₂ alkyloxy group,2-naphtyl-C₁-C₁₂ alkyloxy group, etc.; and preferably C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂ alkyloxy group, and C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkyloxygroup.

The arylalkylthio group may have a substituent, and usually has about 7to 60 carbon atoms. Specifically, exemplified are: phenyl-C₁-C₁₂alkylthio group, C₁-C₁₂ alkyloxy phenyl-C₁-C₁₂ alkylthio group, C₁-C₁₂alkylphenyl-C₁₋C₁₂ alkylthio group, 1-naphtyl-C₁-C₁₂ alkylthio group,2-naphtyl-C₁-C₁₂ alkylthio group, etc.; and preferably C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂ alkylthio group, and C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylthiogroup.

The arylalkylamino group usually has about 7 to 60 carbon atoms.Specifically, exemplified are: phenyl-C₁-C₁₂ alkyl amino group, C₁-C₁₂alkoxyphenyl-C₁-C₁₂ alkylamino group, C₁-C₁₂ alkylphenyl-C₁-C₁₂alkylamino group, di(C₁-C₁₂ alkoxy phenyl-C₁-C₁₂ alkyl)amino group,di(C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkyl)amino group, 1-naphtyl-C₁-C₁₂alkylamino group, 2-naphtyl-C₁-C₁₂ alkylamino group, etc.; andpreferably C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylamino group, and di(C₁-C₁₂alkylphenyl-C₁-C₁₂ alkyl)amino group.

As the substituted silyl group, specifically exemplified are:trialkylsilyl groups, such as trimethylsilyl group, triethylsilyl group,tripropylsilyl group, tri-1-propylsilyl group, dimethyl-1-propylsilylgroup, diethyl-1-propylsilyl group, t-butyldimethylsilyl group,pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group,nonyldimethylsilyl group, decyldimethylsilyl group,3,7-dimethyloctyl-dimethylsilyl group, and lauryldimethylsilyl group,and the like; triarylsilyl groups, such as triphenyl silyl group,tri-p-xylylsilyl group, and the like; tri(arylalkyl)silyl groups, suchas tribenzylsilyl group, and the like; (alkyl)(aryl)silyl groups, suchas diphenylmethylsilyl group, t-butyl diphenylsilyl group,dimethylphenylsilyl group, and the like; mono(arylalkyl)silyl groups,such as phenyl-C₁-C₁₂ alkylsilyl group, C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂alkylsilyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylsilyl group,1-naphtyl-C₁-C₁₂ alkylsilyl group, 2-naphtyl-C₁-C₁₂-alkylsilyl group,and the like; and mono(arylalkyl)dialkylsilyl groups, such asphenyl-C₁-C₁₂ alkyldimethyl silyl group, and the like.

Pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilylgroup, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group,3,7-dimethyloctyldimethylsilyl group, C₁-C₁₂ alkyloxyphenyl-C₁-C₁₂alkylsilyl group, C₁-C₁₂ alkylphenyl-C₁-C₁₂ alkylsilyl group arepreferable.

The acyl group has usually 2 to 20 carbon atoms, and specificallyexemplified are acetyl group, propionyl group, butyryl group, isobutyrylgroup, pivaloyl group, benzoyl group, trifluoroacetyl group,pentafluorobenzoyl group, etc.

The acyloxy group usually has 2 to 20 carbon atoms, and specificallyexemplified are acetyloxy group, propionyloxy group, butyryloxy group,isobutyryloxy group, pivaloyloxy group, benzoyloxy group,trifluoroacetyloxy group, pentafluorobenzoyloxy group, etc.

The imino group usually has about 2 to 20 carbon atoms. Specifically,groups represented by following structural formulas etc. areexemplified.

The amide group usually has 2 to 20 carbon atoms, and specificallyexemplified are formamide group, acetamide group, propioamide group,butyroamide group, benzamide group, trifluoroacetamide group,pentafluorobenzamide group, diformamide group, diacetoamide group,dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, succinimide group,phthalic-imide group, etc.

The arylalkenyl group usually has 7 to 60 carbon atoms, and specificallyexemplified are phenyl-C₂-C₁₂ alkenyl group, C₁-C₁₂alkyloxyphenyl-C₂-C₁₂ alkenyl group, C₁-C₁₂ alkyl phenyl-C₂-C₁₂ alkenylgroup, 1-naphtyl-C₂-C₁₂ alkenyl group, 2-naphtyl-C₂-C₁₂ alkenyl group,etc.; and preferably C₁-C₁₂ alkyloxy phenyl-C₂-C₁₂ alkenyl group, andC₁-C₁₂ alkyl phenyl-C₂-C₁₂ alkenyl group.

The arylalkynyl group usually has 7 to 60 carbon atoms, and specificallyexemplified are phenyl-C₂-C₁₂ alkynyl group, C₁-C₁₂alkyloxyphenyl-C₂-C₁₂ alkynyl groups, C₁-C₁₂ alkyl phenyl-C₂-C₁₂ alkynylgroup, 1-naphtyl-C₂-C₁₂ alkynyl group, 2-naphtyl-C₂-C₁₂ alkynyl group,etc.; and preferably C₁-C₁₂ alkyloxyphenyl-C₂-C₁₂ alkynyl group, andC₁-C₁₂ alkylphenyl-C₂-C₁₂ alkynyl group.

The mono-valent heterocyclic group means an atomic group in which ahydrogen atom is removed from a heterocyclic compound, and usually hasabout 4 to 60 carbon atoms. Specifically, exemplified are: thienylgroup, C₁-C₁₂ alkyl thienyl group pyroryl group, furyl group, pyridylgroup, C₁-C₁₂ alkylpyridyl group, etc.; and preferably thienyl group,C₁-C₁₂ alkylthienyl group, pyridyl group, and C₁-C₁₂ alkylpyridyl group.

Among them, A¹ in the above formula (I) is preferably a divalent grouprepresented by the below formula (4), (5), or (6).

[in the formula, R⁷ represents an alkyl group, alkyloxy group, alkylthiogroup, alkylamino group, aryl group, aryloxy group, arylthio group,arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, arylalkylamino group, acyl group, acyloxy group, amide group, ormonovalent heterocyclic group.]

[in the formula, A² represents Si, Ge, or Sn. R⁸ and R⁹ eachindependently represent alkyl group, alkyloxy group, alkylthio group,alkylamino group, aryl group, aryloxy group, arylthio group, arylaminogroup, arylalkyl group, arylalkyloxy group, arylalkylthio group,arylalkylamino group, acyloxy group, amide group, or monovalentheterocyclic group. 1 represents 1 or 2.]

Among them, in the above formula (1), preferables are: a polymer whoseA¹ is a divalent group represented by the above formula (4); a polymerwhose A¹ is a divalent group represented by the above formula (5); apolymer whose A¹ is a divalent group represented by formula (6), A² isSi, and 1 is 1; and a polymer whose A¹ is a divalent group representedby formula (6), A² is Si, and 1 is 2.

Specific examples of the divalent group whose A¹ is represented by theabove formula (4) include followings.

Specific examples of the divalent group whose A¹ is represented by theabove formula (5) include followings.

Specific examples of the divalent group whose A¹ is represented by theabove formula (6), A² is Si, and l is 1 include followings.

Specific examples of the divalent group whose A¹ is represented by theabove formula (6), A² is Si, and l is 2 include followings.

In the above formula, Me represents a methyl group, Ph represents aphenyl group, Bn represents a benzyl, and Ac represents an acetyl group.

The polymer of the present invention may contain two or more kinds ofrepeating units represented by the above formula (1).

The amount of the repeating unit shown by the above formula (1) isusually 1 to 100% by mole based on the sum of total moles of allrepeating units contained in the polymer of the present invention,preferably 40 to 90% by mole, and more preferably 70 to 85% by mole.

The polymer of the present invention may contain a repeating unit otherthan the repeating unit represented by the above formula (1). As therepeating unit other than formula (1), exemplified are a repeating unitrepresented by the below formula (7), and a repeating unit representedby formula (8) after-mentioned.—Ar⁶—(CR¹⁷═R¹⁸)n—  (7)[in the formula, Ar⁶ represents an arylene group or a divalentheterocyclic group, R¹⁷ and R¹⁸ each independently represent a hydrogenatom, an alkyl group, aryl group, monovalent heterocyclic group, orcyano group; and n represents 0 or 1.]

In view of the life time of a device, the repeating unit represented bythe after-mentioned formula (8) is preferable.

The Ar⁶ may have a substituent, such as an alkyl group, alkyloxy group,alkylthio group, alkylamino group, aryl group, aryloxy group, arylthiogroup, arylamino group, arylalkyl group, arylalkyloxy group,arylalkylthio group, arylalkylamino group, substituted silyl group, acylgroup, acyloxy group, imino group, amide group, imide group, arylalkenylgroup, arylalkynyl group, monovalent heterocyclic group, or cyano group.Specific examples of these substituents represent the same asaforementioned. When Ar⁶ has a plurality of substituents, they may bemutually the same or different.

The arylene group in the present invention includes those containing abenzene ring, a condensed ring, and two or more of independent benzenerings or condensed rings bonded through a group such as a direct bond, avinylene group or the like. The arylene group has usually 6 to 60 carbonatoms, preferably 6 to 20 carbon atoms. As the arylene group,exemplified are phenylene group (for example, following formula (26)),naphthalenediyl group (following formula (27)), anthracenylene group(following formula (28)), biphenylene group (following formula (29)),triphenylene group (following formula (30)), condensed ring compoundgroup (following formula (31)), etc.

In the present invention, the divalent heterocyclic group is an atomicgroup in which two hydrogen atoms are removed from a heterocycliccompound, and usually has 4 to 60 carbon atoms, preferably 4 to 20carbon atoms. They may have a substituent on the hetero-ring and thecarbon atoms of the substituent are not counted as the carbon atoms ofthe heterocyclic group.

The heterocyclic compound means an organic compound having a cyclicstructure in which at least one heteroatom such as oxygen, sulfur,nitrogen, phosphorus, boron, etc. is contained in the cyclic structureas the element other than carbon atoms.

As the divalent heterocyclic compound group, followings are exemplified.

Divalent heterocyclic compound group containing a nitrogen as a heteroatom; pyridine-diyl group (following formula (32)), diaza phenylenegroup (following formula (33)), quinolinediyl group (following formula(34)), quinoxaline diyl group (following formula (35)), acridine diylgroup (following formula (36)), bipyridyl diyl group (following formula(37)), phenanthroline diyl group (following formula (38)), etc.; groupscontaining a hetero atom, such as silicon, nitrogen, sulfur, selenium,etc. and having a fluorene structure (following formula (39));

5 membered-ring heterocyclic compound group containing a hetero atomsuch as silicon, nitrogen, sulfur, selenium, etc. (following formula(40));

5 membered-ring condensation heterocyclic compound group containing ahetero atom such as silicon, nitrogen, sulfur, selenium, etc. (followingformula (41)), benzothiadiazole-4,7-diyl group,benzo-oxadiazole-4,7-diyl group, etc.;

group in which 5 membered ring heterocyclic compound group containingsilicon, nitrogen, sulfur, selenium, etc. as a hetero atom is connectedwith a phenyl group at the a position of the hetero atom to form a dimeror oligomer (following formula (42)); and

group in which 5 membered ring heterocyclic compound group containingsilicon, nitrogen, sulfur, selenium, etc. as a hetero atom is connectedwith a phenyl group at the α position of the hetero atom (followingformula (43)).

In the above formula, R′ each independently represents a hydrogen atom,a halogen atom, an alkyl group, alkyloxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, aryl aminogroup, arylalkyl group, arylalkyloxy group, aryl alkylthio group,arylalkylamino group, acyloxy group, amide group, arylalkenyl group,arylalkynyl group, monovalent heterocyclic group, or cyano group. R″represents a hydrogen atom, an alkyl group, aryl group, arylalkyl group,silyl group, acyl group, or monovalent heterocyclic group.

The divalent heterocyclic group includes, for example, a tripletluminescence complex etc. and the following divalent metal-complexgroups are exemplified.

As the examples of the arylene group or divalent heterocyclic group, thearylene groups or divalent heterocyclic groups contained in thematerials conventionally used as EL luminescence materials are alsoexemplified. These materials are disclosed in, for example, WO 99/12989,WO 00/55927, WO 01/49769A1, WO01/49768A2, WO98/06773, U.S. Pat. No.5,777,070, WO 99/54385, WO 00/46321, and U.S. Pat. No. 6,169,163B1.

The repeating unit other than the repeating unit represented by theabove formula (1), preferably contains a repeating unit represented bythe below formula (8), in view of life time of a device.

[in the formula, Ar¹ and Ar² each independently represent an arylenegroup or divalent heterocyclic group; R¹¹ represents an alkyl group,aryl group, monovalent heterocyclic group, a group represented by thebelow formula (9) or (10); m represents an integer of 1 to 4,

(in the formula, Ar³ represents an arylene group or divalentheterocyclic group; R¹² represents a hydrogen atom, an alkyl group, arylgroup, monovalent heterocyclic group, or a group represented by thebelow formula (10); Y¹ represents—CR³═CR¹⁴—, or —C≡C—; R¹³ and R¹⁴ each independently represent ahydrogen atom, an alkyl group, aryl group, monovalent heterocyclicgroup, or cyano group; p represents an integer of 0-2),

(in the formula, Ar⁴ and Ar⁵ each independently represent an arylenegroup or a divalent heterocyclic group; R¹⁵ represents an alkyl group,aryl group, or monovalent heterocyclic group; R¹⁶ represents a hydrogenatom, an alkyl group, aryl group, or monovalent heterocyclic group; qrepresents an integer of 1 to 4)].

Specific examples of the arylene group, and divalent heterocyclic groupfor Ar¹-Ar⁵ in the above formulas (8)-(10) are the same as thoseaforementioned. Specific examples of the alkyl group, aryl group, andmonovalent heterocyclic group for R¹¹-R¹⁶ in the above formulas (8)-(10)are the same as those aforementioned.

As the preferable examples of the repeating unit represented by theabove formula (8), exemplified are the followings which may have asubstituent on the benzene ring or heterocyclic ring. As thesubstituent, a halogen atom, an alkyl group, alkyloxy group, alkylthiogroup, alkylamino group, aryl group, aryloxy group, arylthio group,arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthiogroup, arylalkylamino group, acyl group, acyloxy group, amide group,imino group, silyl group, silyloxy group, silylthio group, silylaminogroup, monovalent heterocyclic group, arylalkenyl group, arylethynylgroup, and cyano group are exemplified.

The repeating units contained in the polymer of the present inventionmay be connected by non-conjugated units, and may have a non-conjugatedportion in the repeating units themselves.

As the non-conjugated unit, exemplifeid are groups shown below, those inwhich the group shown below is combined with a vinylene groups, andthose in which two of more kinds of the groups shown below are combined.R is a group selected from the group consisting of a hydrogen atom,alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 60carbon atoms, and a heterocyclic group having 4 to 60 carbon atoms, andAr represents a hydrocarbon group having 6 to 60 carbon atoms.

The polymer may also be a random, block or graft copolymer, or a polymerhaving an intermediate structure thereof, for example, a randomcopolymer having block property. From the viewpoint for obtaining apolymer having high fluorescent quantum yield, random copolymers havingblock property and block or graft copolymers are more preferable thancomplete random copolymers. Further, the polymer have a branched mainchain and more than three terminals, and a dendrimer.

The end group of polymer may also be protected with a stable group sinceif a polymerization active group remains intact, there is a possibilityof reduction in light emitting property and life-time when thefluorescent substance is made into an device. Those having a conjugatedbond continuing to a conjugated structure of the main chain arepreferable, and there are exemplified structures connected to an arylgroup or heterocyclic compound group via a carbon-carbon bond.Specifically, substituents of the chemical formula 10 in JP-A No.9-45478 are exemplified.

The polymer has a polystyrene reduced number average molecular weight of10³ to 10⁸. Degree of polymerization thereof changes according to thestructure of the repeating units or the ratio thereof. From theviewpoint of film-molding property, generally the total number ofrepeating units are preferably 20 to 10000, more preferably 30 to 10000,and further preferably 50 to 5000.

As good solvents for the polymer, there are exemplified chloroform,methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene,mesitylene, tetralin, decalin, n-butylbenzene and the like. The polymercan be usually dissolved in these solvents in an amount of 0.1 wt % ormore, though the amount differs depending on the structure and molecularweight of the polymer.

The polymer of the present invention can be manufactured by condensationpolymerization, using a compound represented by the below formula (II).

(in the formula, R¹, R², R³, R⁴, R⁵, R⁶, and A¹ represent the same asthose in formula (1); x¹ and x² each independently represent asubstituent capable of condensation polymerization.)

As the substituents capable of condensation polymerization, exemplifiedare: a halogen atom, alkyl sulfonate group, aryl sulfonate group,arylalkyl sulfonate group, borate group, sulfonium methyl group,phosphonium methyl group, phosphonate methyl group,monohalogenated-methyl group, boric-acid group, formyl group, cyanogroup, vinyl group, etc.; and preferably a halogen atom, alkyl sulfonategroup, aryl sulfonate group, and arylalkyl sulfonate group.

Here, as the alkyl sulfonate group, methane sulfonate group, ethanesulfonate group, trifluoromethane sulfonate group, etc. are exemplified.As the aryl sulfonate group, benzene sulfonate group, p-toluenesulfonate group, etc. are exemplified. As the aryl sulfonate group,benzyl sulfonate group etc. are exemplified.

As the boric-acid ester group, groups represented by the below formulasare exemplified.

In the formula, Me shows a methyl group and Et shows an ethyl group.

As the sulfonium methyl group, groups represented by the below formulasare exemplified.—CH₂S⁺Me₂X⁻, —CH₂S⁺Ph₂X(X shows a halogen atom and Ph shows a phenyl group.)

As the phosphonium methyl group, groups represented by the belowformulas are exemplified.—CH₂P⁺Ph₃X⁻ (X shows a halogen atom)

As the phosphonate methyl group, groups represented by the belowformulas are exemplified. —CH₂PO(OR′)₂ (R′ shows an alkyl group, an arylgroup, or an arylalkyl group.)

As the monohalogenated-methyl group, fluoromethyl group, chloromethylgroup, bromomethyl group, and iodomethyl group are exemplified.

For example, in the above formula (I), a polymer whose A¹ is a divalentgroup represented by the above formula (4) can be manufactured by usinga compound whose A¹ is a divalent group represented by the above formula(4) in the above formula (II).

Moreover, a polymer whose A¹ is a divalent group represented by theabove (5) formula in the above formula (I) can be manufactured, by usinga compound whose A¹ is a divalent group represented by the above (5)formula in the above formula (II).

A polymer whose A¹ is a divalent group represented by the above (6)formula in the above formula (1), A² is Si, and 1 is 1, can bemanufactured by using

a compound whose A¹ is a divalent group represented by the above (6)formula in the above formula (II), and A2 is Si, and l is 1 is used.

Furthermore, a polymer whose A¹ is a divalent group, represented by theabove (6) formula in the above formula (1), A² is Si, and l is 2, can bemanufactured by using a compound whose A¹ is a divalent grouprepresented by the above (6) formula in the above formula (11), and A²is Si, and l is 2 is used.

Moreover, when the polymer of the present invention has a repeating unitother than the repeating unit of formula (1), a condensationpolymerization just can be carried out using together with a monomer asthe repeating unit other than the repeating unit of formula (1).

As the monomer used as the repeating unit other than the repeating unitof formula (1), compounds of the below formulas (7-2) and (8-2) areexemplified, and the below formula (8-2) is preferable.X¹—Ar⁶—(CR¹⁷═CR¹⁸)_(n)—X²  (7-2)(In the formula, Ar⁶, R¹⁷ and R¹⁸ represent the same as those in formula(7); X¹ and X² are the same as those in formula (11); n represents aninteger of 0-1.)

(In the formula, Ar¹, Ar², and R¹¹ represent the same as those informula (8); x¹ and x² represent the same as those in formula (11); mrepresents an integer of 0-4.)

In the manufacture method of the polymer of the present invention, asthe method of carrying out condensation polymerization of a compoundrepresented by the above formula (11) which is a raw material, and amonomer as the repeating unit other than the repeating unit of formula(1), known condensation reactions can be used according to the kind ofsubstituents used for condensation polymerization in each of monomersaccording to requirements.

As a method of producing the polymer of the present invention, forexample, a method described in JP-A No. 5-202355 is exemplified, when avinylene group is contained in the main chain. Namely, there areexemplified methods such as polymerization of a compound having a formylgroup with a compound having a phosphonium methyl group, or of acompound having a formyl group and a phosphonium methyl group, accordingto a Wittig reaction, polymerization of a compound having a vinyl groupwith a compound having a halogen atom, according to a Heck reaction,polycondensation of a compound having two or more halogenated methylgroups, according to a de-hydrohalogenating method, polycondensation ofa compound having two or more sulfonium salt groups, according to asulfonium salt-decomposing method, polymerization of a compound having aformyl group with a compound having a cyano group, according to aKnoevenagel reaction, polymerization of a compound having two or moreformyl groups, according to McMurry reaction, and the like.

When a vinylene group is not contained in the main chain, for example, amethod of polymerization from corresponding monomers by a Suzukicoupling reaction, a method of polymerization by a Grignard reaction, amethod of polymerization using a Ni(0) catalyst, a method ofpolymerization using an oxidizer such as FeCl₃ and the like, a method ofoxidation polymerization electrochemically, a method of decomposition ofan intermediate polymer having a suitable releasing group, and the likeare exemplified.

Of these, the polymerization method by a Wittig reaction, thepolymerization method by a Heck reaction, the polymerization method by aHorner-Wadsworth-Emmons method, the polymerization method by aKnoevenagel reaction, the polymerization method by a Suzuki couplingreaction, the polymerization method by a Grignard reaction and thepolymerization method using a Ni(0) catalyst are preferable sincestructure control is easy in these methods.

Among the manufacture methods of the present invention, it is suitableto conduct a condensation polymerization of a compound as a monomerrepresented by the above formula (II) in which x¹ and x² are eachindependently a halogen atom, alkyl sulfonate group, aryl sulfonategroup or arylalkyl sulfonate group, preferably a halogen atom, using apalladium catalyst or a nickel catalyst.

In the manufacture method of the present invention, the compound of theabove formula (11) used as raw material monomer, and a monomer, such asthe above formula (7-2) or a formula (8-2) are, if necessary, dissolvedin an organic solvent, and reacted at a temperature of below the boilingpoint and above the melting point of the organic solvent, using analkali or a suitable catalyst, if necessary. For example, known methodscan be used, described in “Organic Reactions”, vol. 14, pp. 270 to 490,John Wiley & Sons, Inc., 1965, “Organic Reactions”, vol. 27, pp. 345 to390, John Wiley & Sons, Inc., 1982, “Organic Synthesis”, CollectiveVolume VI, pp. 407 to 411, John Wiley & Sons, Inc., 1988, ChemicalReview, vol. 95, p. 2457 (1995), Journal of Organometallic Chemistry,vol. 576, p. 147 (1999), Journal of Praktical Chemistry, vol. 336, p.247 (1994), Makromolecular Chemistry Macromolecular Symposium, vol. 12,p. 229 (1987), and the like.

It is preferable that the organic solvent used is subjected to adeoxygenation treatment sufficiently and the reaction is progressedunder an inert atmosphere, generally for suppressing a side reaction,though the treatment differs depending on compounds and reactions used.Further, it is preferable to conduct a dehydration treatment likewise(however, this is not applicable in the case of a reaction in atwo-phase system with water, such as a Suzuki coupling reaction).

In order to promote the reaction, an alkali or a catalyst is addedappropriately. These may be selected according to the reaction. It ispreferable that the alkali or catalyst is soluble sufficiently in asolvent used for the reaction. As the method of mixing an alkali orcatalyst, there is exemplified a method of adding a solution of analkali or catalyst slowly while stirring under an inner atmosphere ofargon and nitrogen and the like or a method of slowly adding thereaction solution to a solution of an alkali or catalyst, inversely.

It is preferable to polymerize, after purifying the monomer before apolymerization by methods, such as distillation, sublimationpurification, and recrystallization, since the purity may affect theperformance of devices, such as luminescence characteristics, when usingthe polymer of the present invention for polymer LED. Moreover, it ispreferable to carry out purification processing such as reprecipitationpurification, and fractionation by chromatography etc. afterpolymerization.

A compound represented by the below formula (12) which is a divalentgroup whose A¹ in the above formula (11) is represented by the above (4)formula,

can be prepared by: after metalating the two iodine atoms of thecompound below formula (13) selectively,

[in the formula, R¹, R², R³, R⁴, R⁵, R⁶, x¹ and x² represent the same asthe above], and reacting it with a dihalogenated phosphorous compoundrepresented by the below formula (14),

[in the formula, R⁷ represents the same as the above; x5 and x6 eachindependently represents a chlorine atom, a bromine atom, or an iodineatom.]

The reaction can be carried out under inert atmospheres, such asnitrogen and argon, in the presence of a solvent. As the solvent usedfor reaction, exemplified are: saturated hydrocarbons, such as pentane,hexane, heptane, octane, and cyclohexane; unsaturated hydrocarbons, suchas benzene, toluene, xylene, and ethylbenzene; ethers, such as dimethylether, diethyl ether, methyl-t-butyl ether, di-t-butyl ether,tetrahydrofuran, tetrahydropyran, and dioxane; and amines, such astrimethylamine, triethylamine, N,N,N′,N′-tetramethylethylenediamine, andpyridine. These may be used as alone or a mixture thereof.

As the metalating agent, methyl lithium, n-butyl lithium, sec-butyllithium, t-butyl lithium, phenyl lithium, etc. are exemplified. Thereaction temperature is usually −30° C. or less, and preferably −80° C.or less in order to metalate selectively.

Moreover, it may be reacted with the dihalogenated phosphorous compoundrepresented by the above formula (14) after exchanging the metal of thecompound metalated by the above method.

As the metal exchanging reagent, magnesium salts, such as magnesiumchloride and a magnesium bromide; copper salt, such as copper chloride(I), copper chloride (II), copper bromide (I), copper bromide (II), andcopper iodide (I); and zinc salts, such as zinc chloride, and zincbromide, and zinc iodide, are exemplified. In view of yield, magnesiumsalt is preferable.

As for the reaction with a dihalogenated phosphorous compoundrepresented by the above formula (14), it is preferable to carry out atfrom −100° C. to the boiling point of a solvent.

After the reaction, it can be obtained by a usual post-treatment, forexample, quenching with water, then extracting by an organic solvent,and distilling of the solvent. When the product is unstable to water, itcan be obtained by a method of distilling a solvent after removinginorganic salt by filtration.

Isolation and purification of the product can be performed by a method,such as recrystallization, distillation, or fractionation bychromatography.

Moreover, a compound represented the below formula (15) whose A¹ is adivalent group represented by the above formula (5) in the above formula(11),

can be manufactured by: after metalating the two iodine atoms of thecompound represented by the above formula (13), and reacting it withsulfur.

About the reaction method, it is the same as that of the syntheticprocess of the compound represented by the above formula (12). About thereaction with sulfur, it may be added as any form of solid, or dissolvedor suspended in a solvent. The temperature of the reaction is from −100°C. to 30° C., and preferably from −80° C. to 0° C. About thepost-treatment of reaction, and the purification method, it is also thesame as that of the compound represented by the above formula (12).

A compound represented by the below formula (20) whose A¹ is a divalentgroup represented by the above formula (6) in the above formula (11),and A² is Si, and l is 2,

can be manufactured by: after metalating the two iodine atoms of thecompound represented by the above formula (13), and reacting it with1,2-dihalogenated disilyl compound represented by the below formula(22),

[in the formula, R⁸ and R⁹ represent the same as the above. x11 and x12each independently represent a chlorine atom, a bromine atom, or aniodine atom.]

About the reaction method, post-treatment, and purification method, itis the same as those of the compound represented by the above formula(12).

Moreover, similarly with the compound represented by the above formula(12), the compound represented by the below formula (3-2) can bemanufactured by reacting it with the dihalogenated compound aftermetalating the two iodine atoms of the compound represented by the aboveformula (13) selectively. About the method of reaction, post-treatment,and purification method, it is the same as those of the compoundrepresented by the above formula (12).

(In the formula, R¹, R², R³, R⁴, R⁵, and R⁶ represent the same as thosein formula (11). x¹ and x² are represent the same as those in formula(11). A³ represents a divalent group selected from

In the formula, R represents the same as aforementioned.) About thereaction method, post-treatment, and purification method, it is the sameas those of the compound represented by the above formula (12).

A dibenzosilole derivative represented by the below formula (18) whoseA¹ is a divalent group represented by the above formula (6) in the aboveformula (11), and A² is Si, and l is 1,

can be manufactured by reacting a compound (dibenzosilole derivative)represented by the below formula (19), with a halogenation reagent,preferably an N-halogeno compound,

(in the formula, R¹, R², R³, R⁴, R⁵, R⁶, R⁸, and R⁹ represent the sameas those in formula (II).)

The reaction can be carried out under inert atmosphere such as nitrogenand argon, in the presence of a solvent. The reaction temperature ispreferably from −80° C. to the boiling point of the solvent.

Moreover, it can be manufactured also by a method in which ahalogenation reagent is reacted, after reacting the compound representedby formula (19) with a base.

As the N-halogeno compound, N-chloro succinimide, N-chloro phthalicimide, N-chloro diethylamine, N-chloro dibutyl amine, N-chlorocyclohexyl amine, N-bromosuccinimide, N-bromo phthalic-imide, N-bromoditrifluoromonomethylamine, N-iodo succinimide, N-iodophthalic imide,etc. are exemplified. As the other halogenation reagents, fluorine,fluoroxy trifluoromethane, oxygen difluoride, perchloryl fluoride,cobalt fluoride (III), silver fluoride (II), selenium fluoride (IV),manganese fluoride (III), chlorine, iodine trichloride, aluminumtrichloride, tellurium chloride (IV), molybdenum chloride, antimonychloride, iron chloride (III), titanium tetrachloride, phosphoruspentachloride, thionyl chloride, bromine, 1,2-dibromo ethane, borontribromide, copper bromide, silver bromide, t-butyl bromide, bromineoxide, iodine, iodine monochloride, etc. are exemplified.

As the solvent used for reaction, exemplified are: saturatedhydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane;unsaturated hydrocarbons, such as benzene, toluene, ethylbenzene,xylene; halogenated saturated hydrocarbons, such as carbontetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane,chloropentane, bromopentane, chlorohexane, bromohexane,chlorocyclohexane, and bromocyclohexane; halogenated unsaturatedhydrocarbons, such as chlorobenzene, dichlorobenzene, andtrichlorobenzene; alcohols, such as methanol, ethanol, propanol,isopropanol, butanol, t-butyl alcohol; carboxylic acids, such as, formicacid, acetic acid, and propionic acid; ethers, such as, dimethyl ether,diethyl ether, methyl-t-butyl ether, tetrahydrofuran, tetrahydropyran,and dioxane; amines, such as trimethylamine, triethylamine,N,N,N′,N′-tetramethylethylenediamine, and pyridine; amides, such as,N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethyl acetamide,N-methylmorpholine oxide, and N-methyl-2-pyrrolidone. These may be usedalone or a mixture thereof.

As the base used for reaction, exemplified are: lithium hydride, sodiumhydride, potassium hydride, methyl lithium, n-butyl lithium, t-butyllithium, phenyl lithium, lithium diisopropyl amide, lithiumhexamethyldisilazide, sodium hexa methyldisilazide, potassium hexamethyldisilazide, etc.

After the reaction, it can be obtained by a usual post-treatment, forexample, quenching with water, then extracting by an organic solvent,and distilling of the solvent.

Isolation and purification of the product can be performed by a method,such as recrystallization, distillation, or fractionation bychromatography.

Next, the use of the polymer of the present invention is explained.

The polymer of the present invention has strong fluorescence, and it canbe used as a polymeric fluorescent substance. Moreover, since theluminescence from a thin film is used, polymeric fluorescent substanceshaving fluorescence in the solid state are used preferably. Moreover,the polymer has excellent electronic transporting property, and can beused suitably as a polymer LED material, or a charge transportingmaterial. The polymer of the present invention can be used also as amaterial for electronic devices, and can be used also as a coloringmatter for lasers, a solar-battery material, an organic semiconductorfor organic transistors, and a conductive thin-film material.

Next, the polymer LED of the present invention will be described. Thepolymer LED of the present invention, has a light-emitting layer betweenan anode and a cathode, and the polymer of the present invention iscontained in the light-emitting layer.

As the polymer LED of the present invention, there are listed polymerLEDs having an electron transporting layer disposed between a cathodeand a light emitting layer, polymer LEDs having a hole transportinglayer disposed between an anode and a light emitting layer, polymer LEDshaving an electron transporting layer disposed between a cathode and alight emitting layer and having a hole transporting layer disposedbetween an anode and a light emitting layer.

Moreover, as the polymer LED of the present invention, there areexemplified: a device having a layer containing a conducting polymerdisposed between at least one of the electrodes and a light emittinglayer, adjacently to said electrode; and a device having an insulatinglayer having a thickness of 2 nm or less disposed between at least oneof the electrodes and a light emitting layer, adjacently to saidelectrode.

For example, the following structures a) to d) are specificallyexemplified.

a) anode/light emitting layer/cathode

b) anode/hole transporting layer/light emitting layer/cathode

c) anode/light emitting layer/electron transporting layer/cathode

d) anode/hole transporting layer/light emitting layer/electrontransporting layer/cathode

(wherein, “/” indicates adjacent lamination of layers.)

Herein, the light emitting layer is a layer having function to emit alight, the hole transporting layer is a layer having function totransport a hole, and the electron transporting layer is a layer havingfunction to transport an electron. Herein, the electron transportinglayer and the hole transporting layer are generically called a chargetransporting layer. The light emitting layer, hole transporting layerand electron transporting layer may also each independently used in twoor more layers.

Of charge transporting layers disposed adjacent to an electrode, thathaving function to improve charge injecting efficiency from theelectrode and having effect to decrease driving voltage of an device areparticularly called sometimes a charge injecting layer (hole injectinglayer, electron injecting layer) in general.

For enhancing adherence with an electrode and improving charge injectionfrom an electrode, the above charge injecting layer or insulation layerhaving a thickness of 2 nm or less may also be provided adjacent to anelectrode, and further, for enhancing adherence of the interface,preventing mixing and the like, a thin buffer layer may also be insertedinto the interface of a charge transporting layer and light emittinglayer.

The order and number of layers laminated and the thickness of each layercan be appropriately applied while considering light emitting efficiencyand life of the device.

In the present invention, as the polymer LED having a charge injectinglayer (electron injecting layer, hole injecting layer) provided, thereare listed a polymer LED having a charge injecting layer providedadjacent to a cathode and a polymer LED having a charge injecting layerprovided adjacent to an anode.

For example, the following structures e) to p) are specificallyexemplified.

e) anode/charge injecting layer/light emitting layer/cathode

f) anode/light emitting layer/charge injecting layer/cathode

g) anode/charge injecting layer/light emitting layer/charge injectinglayer/cathode

h) anode/charge injecting layer/hole transporting layer/light emittinglayer/cathode

i) anode/hole transporting layer/light emitting layer/charge injectinglayer/cathode

j) anode/charge injecting layer/hole transporting layer/light emittinglayer/charge injecting layer/cathode

k) anode/charge injecting layer/light emitting layer/electrontransporting layer/cathode

l) anode/light emitting layer/electron transporting layer/chargeinjecting layer/cathode

m) anode/charge injecting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

n) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/cathode

o) anode/hole transporting layer/light emitting layer/electrontransporting layer/charge injecting layer/cathode

p) anode/charge injecting layer/hole transporting layer/light emittinglayer/electron transporting layer/charge injecting layer/cathode

As the specific examples of the charge injecting layer, there areexemplified: layers containing an conducting polymer; layers which aredisposed between an anode and a hole transporting layer and contain amaterial having an ionization potential between the ionization potentialof an anode material and the ionization potential of a hole transportingmaterial contained in the hole transporting layer, and the like.

When the above charge injecting layer is a layer containing anconducting polymer, the electric conductivity of the conducting polymeris preferably 10⁻⁵ S/cm or more and 103 S/cm or less, and for decreasingthe leak current between light emitting pixels, more preferably 10⁻⁵S/cm or more and 10² S/cm or less, further preferably 10⁻⁵ S/cm or moreand 10¹ S/cm or less.

Usually, to provide an electric conductivity of the conducting polymerof 10⁻⁵ S/cm or more and 10³ S/cm or less, a suitable amount of ions aredoped into the conducting polymer.

Regarding the kind of an ion to be doped, an anion is used for a holeinjecting layer and a cation is used for an electron injecting layer. Asexamples of the anion, a polystyrene sulfonate ion, alkylbenzenesulfonate ion, camphor sulfonate ion and the like are exemplified, andas examples of the cation, a lithium ion, sodium ion, potassium ion,tetrabutyl ammonium ion and the like are exemplified.

The thickness of the charge injecting layer is for example, from 1 nm to100 nm, preferably from 2 nm to 50 nm.

Materials used in the charge injecting layer may be selectedappropriately according to the relation with the electrode materials andadjacent layers, and there are exemplified conducting polymers such aspolyaniline and derivatives thereof, polythiophene and derivativesthereof, polypyrrole and derivatives thereof, poly(phenylene vinylene)and derivatives thereof, poly(thienylene vinylene) and derivativesthereof, polyquinoline and derivatives thereof, polyquinoxaline andderivatives thereof, polymers containing aromatic amine structures inthe main chain or the side chain, and the like, and metal phthalocyanine(copper phthalocyanine and the like), carbon and the like.

The insulation layer having a thickness of 2 nm or less has function tomake charge injection easy. As the material of the above insulationlayer, metal fluoride, metal oxide, organic insulation materials and thelike are listed. As the polymer LED having an insulation layer having athickness of 2 nm or less, there are listed polymer LEDs having aninsulation layer having a thickness of 2 nm or less provided adjacent toa cathode, and polymer LEDs having an insulation layer having athickness of 2 nm or less provided adjacent to an anode.

Specifically, there are listed the following structures q) to ab) forexample.

q) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/cathode

r) anode/light emitting layer/insulation layer having a thickness of 2nm or less/cathode

s) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/insulation layer having a thickness of 2 nm orless/cathode

t) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/cathode

u) anode/hole transporting layer/light emitting layer/insulation layerhaving a thickness of 2 nm or less/cathode

v) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/insulation layer having athickness of 2 nm or less/cathode

w) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/cathode

x) anode/light emitting layer/electron transporting layer/insulationlayer having a thickness of 2 nm or less/cathode

y) anode/insulation layer having a thickness of 2 nm or less/lightemitting layer/electron transporting layer/insulation layer having athickness of 2 nm or less/cathode

z) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/cathode

aa) anode/hole transporting layer/light emitting layer/electrontransporting layer/insulation layer having a thickness of 2 nm orless/cathode

ab) anode/insulation layer having a thickness of 2 nm or less/holetransporting layer/light emitting layer/electron transportinglayer/insulation layer having a thickness of 2 nm or less/cathode

In producing a polymer LED, when a film is formed from a solution byusing such polymer soluble in an organic solvent, only required isremoval of the solvent by drying after coating of this solution, andeven in the case of mixing of a charge transporting material and a lightemitting material, the same method can be applied, causing an extremeadvantage in production. As the film forming method from a solution,there can be used coating methods such as a spin coating method, castingmethod, micro gravure coating method, gravure coating method, barcoating method, roll coating method, wire bar coating method, dipcoating method, spray coating method, screen printing method, flexoprinting method, offset printing method, inkjet printing method and thelike.

Regarding the thickness of the light emitting layer, the optimum valuediffers depending on material used, and may properly be selected so thatthe driving voltage and the light emitting efficiency become optimumvalues, and for example, it is from 1 nm to 1 μm, preferably from 2 nmto 500 nm, further preferably from 5 nm to 200 nm.

In the polymer LED of the present invention, light emitting materialsother than the above polymeric fluorescent substance can also be mixedin a light emitting layer. Further, in the polymer LED of the presentinvention, the light emitting layer containing light emitting materialsother than the above polymeric fluorescent substance may also belaminated with a light emitting layer containing the above polymericfluorescent substance.

As the light emitting material, known materials can be used. In acompound having lower molecular weight, there can be used, for example,naphthalene derivatives, anthracene or derivatives thereof, perylene orderivatives thereof; dyes such as polymethine dyes, xanthene dyes,coumarine dyes, cyanine dyes; metal complexes of 8-hydroxyquinoline orderivatives thereof, aromatic amine, tetraphenylcyclopentane orderivatives thereof, or tetraphenylbutadiene or derivatives thereof, andthe like.

Specifically, there can be used known compounds such as those describedin JP-A Nos. 57-51781, 59-195393 and the like, for example.

When the polymer LED of the present invention has a hole transportinglayer, as the hole transporting materials used, there are exemplifiedpolyvinylcarbazole or derivatives thereof, polysilane or derivativesthereof, polysiloxane derivatives having an aromatic amine in the sidechain or the main chain, pyrazoline derivatives, arylamine derivatives,stilbene derivatives, triphenyldiamine derivatives, polyaniline orderivatives thereof, polythiophene or derivatives thereof, polypyrroleor derivatives thereof, poly(p-phenylenevinylene) or derivativesthereof, poly(2,5-thienylenevinylene) or derivatives thereof, or thelike.

Specific examples of the hole transporting material include thosedescribed in JP-A Nos. 63-70257, 63-175860, 2-135359, 2-135361,2-209988, 3-37992 and 3-152184.

Among them, as the hole transporting materials used in the holetransporting layer, preferable are polymer hole transporting materialssuch as polyvinylcarbazole or derivatives thereof, polysilane orderivatives thereof, polysiloxane derivatives having an aromatic aminecompound group in the side chain or the main chain, polyaniline orderivatives thereof, polythiophene or derivatives thereof,poly(p-phenylenevinylene) or derivatives thereof,poly(2,5-thienylenevinylene) or derivatives thereof, or the like, andfurther preferable are polyvinylcarbazole or derivatives thereof,polysilane or derivatives thereof and polysiloxane derivatives having anaromatic amine compound group in the side chain or the main chain. Inthe case of a hole transporting material having lower molecular weight,it is preferably dispersed in a polymer binder for use.

Polyvinylcarbazole or derivatives thereof are obtained, for example, bycation polymerization or radical polymerization from a vinyl monomer.

As the polysilane or derivatives thereof, there are exemplifiedcompounds described in Chem. Rev., 89, 1359 (1989) and GB 2300196published specification, and the like. For synthesis, methods describedin them can be used, and a Kipping method can be suitably usedparticularly.

As the polysiloxane or derivatives thereof, those having the structureof the above hole transporting material having lower molecular weight inthe side chain or main chain, since the siloxane skeleton structure haspoor hole transporting property. Particularly, there are exemplifiedthose having an aromatic amine having hole transporting property in theside chain or main chain.

The method for forming a hole transporting layer is not restricted, andin the case of a hole transporting layer having lower molecular weight,a method in which the layer is formed from a mixed solution with apolymer binder is exemplified. In the case of a polymer holetransporting material, a method in which the layer is formed from asolution is exemplified.

The solvent used for the film forming from a solution is notparticularly restricted providing it can dissolve a hole transportingmaterial. As the solvent, there are exemplified chlorine solvents suchas chloroform, methylene chloride, dichloroethane and the like, ethersolvents such as tetrahydrofuran and the like, aromatic hydrocarbonsolvents such as toluene, xylene and the like, ketone solvents such asacetone, methyl ethyl ketone and the like, and ester solvents such asethyl acetate, butyl acetate, ethylcellosolve acetate and the like.

As the film forming method from a solution, there can be used coatingmethods such as a spin coating method, casting method, micro gravurecoating method, gravure coating method, bar coating method, roll coatingmethod, wire bar coating method, dip coating method, spray coatingmethod, screen printing method, flexo printing method, offset printingmethod, inkjet printing method and the like, from a solution.

The polymer binder mixed is preferably that does not disturb chargetransport extremely, and that does not have strong absorption of avisible light is suitably used. As such polymer binder, polycarbonate,polyacrylate, poly(methyl acrylate), poly(methyl methacrylate),polystyrene, poly(vinyl chloride), polysiloxane and the like areexemplified.

Regarding the thickness of the hole transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe hole transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from 5 nm to 200 nm.

When the polymer LED of the present invention has an electrontransporting layer, known compounds are used as the electrontransporting materials, and there are exemplified oxadiazolederivatives, anthraquinonedimethane or derivatives thereof, benzoquinoneor derivatives thereof, naphthoquinone or derivatives thereof,anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane orderivatives thereof, fluorenone derivatives, diphenyldicyanoethylene orderivatives thereof, diphenoquinone derivatives, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof, and the like.

Specifically, there are exemplified those described in JP-A Nos.63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and 3-152184.

Among them, oxadiazole derivatives, benzoquinone or derivatives thereof,anthraquinone or derivatives thereof, or metal complexes of8-hydroxyquinoline or derivatives thereof, polyquinoline and derivativesthereof, polyquinoxaline and derivatives thereof, polyfluorene orderivatives thereof are preferable, and2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone,anthraquinone, tris(8-quinolinol)aluminum and polyquinoline are furtherpreferable.

The method for forming the electron transporting layer is notparticularly restricted, and in the case of an electron transportingmaterial having lower molecular weight, a vapor deposition method from apowder, or a method of film-forming from a solution or melted state isexemplified, and in the case of a polymer electron transportingmaterial, a method of film-forming from a solution or melted state isexemplified, respectively. At the time of film forming from a solutionor a molten state, a polymer binder can be used together.

The solvent used in the film-forming from a solution is not particularlyrestricted provided it can dissolve electron transporting materialsand/or polymer binders. As the solvent, there are exemplified chlorinesolvents such as chloroform, methylene chloride, dichloroethane and thelike, ether solvents such as tetrahydrofuran and the like, aromatichydrocarbon solvents such as toluene, xylene and the like, ketonesolvents such as acetone, methyl ethyl ketone and the like, and estersolvents such as ethyl acetate, butyl acetate, ethylcellosolve acetateand the like.

As the film-forming method from a solution or melted state, there can beused coating methods such as a spin coating method, casting method,micro gravure coating method, gravure coating method, bar coatingmethod, roll coating method, wire bar coating method, dip coatingmethod, spray coating method, screen printing method, flexo printingmethod, offset printing method, inkjet printing method and the like.

The polymer binder to be mixed is preferably that which does notextremely disturb a charge transport property, and that does not havestrong absorption of a visible light is suitably used. As such polymerbinder, poly(N-vinylcarbazole), polyaniline or derivatives thereof,polythiophene or derivatives thereof, poly(p-phenylene vinylene) orderivatives thereof, poly(2,5-thienylene vinylene) or derivativesthereof, polycarbonate, polyacrylate, poly(methyl acrylate), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), polysiloxane and thelike are exemplified.

Regarding the thickness of the electron transporting layer, the optimumvalue differs depending on material used, and may properly be selectedso that the driving voltage and the light emitting efficiency becomeoptimum values, and at least a thickness at which no pin hole isproduced is necessary, and too large thickness is not preferable sincethe driving voltage of the device increases. Therefore, the thickness ofthe electron transporting layer is, for example, from 1 nm to 1 μm,preferably from 2 nm to 500 nm, further preferably from 5 nm to 200 nm.

The substrate forming the polymer LED of the present invention maypreferably be that does not change in forming an electrode and layers oforganic materials, and there are exemplified glass, plastics, polymerfilm, silicon substrates and the like. In the case of a opaquesubstrate, it is preferable that the opposite electrode is transparentor semitransparent.

In the present invention, at least one of an anode or a cathode istransparent or semitransparent, and it is preferable that the anode istransparent or semitransparent. As the material of this anode, electronconductive metal oxide films, semitransparent metal thin films and thelike are used. Specifically, there are used indium oxide, zinc oxide,tin oxide, and films (NESA and the like) fabricated by using an electronconductive glass composed of indium-tin-oxide (ITO), indium.zinc.oxideand the like, which are metal oxide complexes, and gold, platinum,silver, copper and the like are used, and among them, ITO,indium.zinc.oxide, tin oxide are preferable. As the fabricating method,a vacuum vapor deposition method, sputtering method, ion plating method,plating method and the like are used. As the anode, there may also beused organic transparent conducting films such as polyaniline orderivatives thereof, polythiophene or derivatives thereof and the like.

The thickness of the anode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

Further, for easy charge injection, there may be provided on the anode alayer comprising a phthalocyanine derivative conducting polymers, carbonand the like, or a layer having an average film thickness of 2 nm orless comprising a metal oxide, metal fluoride, organic insulatingmaterial and the like.

As the material of a cathode used in the polymer LED of the presentinvention, that having lower work function is preferable. For example,there are used metals such as lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium, barium, aluminum,scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium,terbium, ytterbium and the like, or alloys comprising two of more ofthem, or alloys comprising one or more of them with one or more of gold,silver, platinum, copper, manganese, titanium, cobalt, nickel, tungstenand tin, graphite or graphite intercalation compounds and the like.Examples of alloys include a magnesium-silver alloy, magnesium-indiumalloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminumalloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminumalloy and the like. The cathode may be formed into a laminated structureof two or more layers.

The thickness of the cathode can be appropriately selected whileconsidering transmission of a light and electric conductivity, and forexample, from 10 nm to 10 μm, preferably from 20 nm to 1 μm, furtherpreferably from 50 nm to 500 nm.

As the method for fabricating a cathode, there are used a vacuum vapordeposition method, sputtering method, lamination method in which a metalthin film is adhered under heat and pressure, and the like. Further,there may also be provided, between a cathode and an organic layer, alayer comprising an conducting polymer, or a layer having an averagefilm thickness of 2 nm or less comprising a metal oxide, metal fluoride,organic insulation material and the like, and after fabrication of thecathode, a protective layer may also be provided which protects thepolymer LED. For stable use of the polymer LED for a long period oftime, it is preferable to provide a protective layer and/or protectivecover for protection of the device in order to prevent it from outsidedamage.

As the protective layer, there can be used a polymer, metal oxide, metalfluoride, metal borate and the like. As the protective cover, there canbe used a glass plate, a plastic plate the surface of which has beensubjected to lower-water-permeation treatment, and the like, and thereis suitably used a method in which the cover is pasted with an devicesubstrate by a thermosetting resin or light-curing resin for sealing. Ifspace is maintained using a spacer, it is easy to prevent an device frombeing injured. If an inner gas such as nitrogen and argon is sealed inthis space, it is possible to prevent oxidation of a cathode, andfurther, by placing a desiccant such as barium oxide and the like in theabove space, it is easy to suppress the damage of an device by moistureadhered in the production process. Among them, any one means or more arepreferably adopted.

The polymer LED of the present invention can be suitably used as a flatlight source, segment display apparatus, dot-matrix display apparatus,and back light of a liquid crystal display.

For obtaining light emission in plane form using the polymer LED of thepresent invention, an anode and a cathode in the plane form may properlybe placed so that they are laminated each other. Further, for obtaininglight emission in pattern form, there are a method in which a mask witha window in pattern form is placed on the above plane light emittingdevice, a method in which an organic layer in non-light emission part isformed to obtain extremely large thickness providing substantialnon-light emission, and a method in which any one of an anode or acathode, or both of them are formed in the pattern. By forming a patternby any of these methods and by placing some electrodes so thatindependent on/off is possible, there is obtained a display device ofsegment type which can display digits, letters, simple marks and thelike. Further, for forming a dot matrix device, it may be advantageousthat anodes and cathodes are made in the form of stripes and placed sothat they cross at right angles. By a method in which a plurality ofkinds of polymers emitting different colors of lights are placedseparately or a method in which a color filter or luminescenceconverting filter is used, area color displays and multi color displaysare obtained. A dot matrix display can be driven by passive driving, orby active driving combined with TFT and the like. These display devicescan be used as a display of a computer, television, portable terminal,portable telephone, car navigation, view finder of a video camera, andthe like.

Further, the above light emitting device in plane form is a thinself-light-emitting one, and can be suitably used as a flat light sourcefor back-light of a liquid crystal display, or as a flat light sourcefor illumination. Further, if a flexible plate is used, it can also beused as a curved light source or a display.

EXAMPLES

Hereafter, examples are shown in order to explain the present inventionin detail, but the present invention should not be construed to belimited thereto.

In the examples, the number average molecular weight and the weightaverage molecular weight were determined by gel permeationchromatography (GPC) using chloroform solvent as the polystyrene reducednumber average molecular weight and the weight average molecular weight,respectively.

Synthetic Example 1 Synthesis of2,2′-dibromo-5,5′-dioctyloxy-1,1′-biphenyl

3,3′-dioctyloxy-1,1′-biphenyl which is a raw material was synthesized byYamamoto coupling, after dioctylation of 3-bromophenol in ethanol.

The above 3,3′-dioctyloxy-1,1′-biphenyl 133 g was dissolved in driedN,N-dimethylformamide 1820 ml. At 00 (dry ice-methanol bath), a solutionof N-bromosuccinimide 117.5 g/N,N-dimethylformamide 910 ml was addeddropwise for 60 minutes. After the dropwise adding, the reaction liquidwas brought back to a room temperature and stirred overnight. Thereaction liquid was charged into water and extracted with n-hexane, andthen the solvent was distilled off and 179 g of crude product wasobtained. ecrystallization was repeated using 2-propanol, and 122 g of2,2′-dibromo-5,5′-dioctyloxy-1,1′-biphenyl was obtained. ¹H-NMR (300MHz/CDCl₃): δ (ppm)=0.88 [t, 6H], 1.2˜1.8 [m, 24H], 3.95 [t, 4H],6.7˜6.8 [m, 4H], 7.52 [d, 2H]

Synthetic Example 2 Synthesis of2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl

Flaky magnesium 4.05 g was put in a 500 ml three-necked flask undernitrogen atmosphere. Tetrahydrofuran solution 200 ml of the above2,2′-dibromo-5,5′-dioctyloxy-1,1′-biphenyl 45 g was prepared in anotherflask, and 20 ml of the solution was added in the flask containingmagnesium. Five drops of 1,2-dibromoethane as the initiator was added,and heated. When the exothermic reaction started, the remaining solutionwas added dropwise for 30 minutes. After the dropwise addition, thereaction was conducted for 1 hour with refluxing. Then, it was cooled to0° C., and tetrahydrofuran 150 ml solution of iodine 44.2 g was addeddropwise. After the dropwise adding, the reaction liquid was stirredovernight.

The reaction liquid was charged into water and extracted withchloroform, and washed with sodium-thiosulfate aqueous solution andsaturated NaCl aqueous solution. After being dried with sodium sulfate,the solvent was distilled off, and 53 g of crude product was obtained.

By recrystallization using 2-propanol, 43 g of2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl was obtained.

¹H-NMR (200 MHz/CDCl₃): δ (ppm)=0.90 [t, 6H], 1.2˜1.8 [m, 24H], 3.93 [t,4H], 6.6˜6.8 [m, 4H], 7.74 [d, 2H]

MS (APCI(+)):M⁺ 662

Synthetic Example 3 Synthesis of4,4′-dibromo-2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl

The above 2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl 37 g was chargedinto 1 L flask under nitrogen atmosphere, and trimethyl phosphate 800 mlwas added and dissolved. Iodine 10.6 g was further added, trimethylphosphate 70 ml of bromine 19 g was added dropwise. After stirring for 4hours, trimethyl phosphate 35 ml of bromine 9.5 g was added dropwise.Then, it was stirred overnight. The reaction liquid was charged intowater and extracted with chloroform, and washed with sodium-thiosulfateaqueous solution and saturated NaCl aqueous solution. After being driedwith sodium sulfate, the solvent was distilled off, and 46 g of crudeproduct was obtained. By purification using silica gel chromatography(cyclohexane:toluene=20:1),4,4′-dibromo-2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl 20.5 g wasobtained.

¹H-NMR (200 MHz/CDCl₃): δ (ppm)=0.88 [t, 6H], 1.2˜1.9 [m, 24H], 3.99 [m,4H], 6.70 [s, 2H], 8.03 [s, 2H]

MS (APCI(+)):M⁺ 820

Synthetic Example 4 Synthesis of Compound A

The above 4,4′-dibromo-2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl 1.00 g(appearance mole number 1.22 mmols) was put in a 100 ml three-neckedflask which was flame dried and argon gas substituted, and dissolved indehydrated diethyl ether 10 ml. This solution was cooled to −90° C. bymethanol/liquid nitrogen, and n-BuLi 1.7 ml (1.6M n-hexane solution, 2.7mmol) was added dropwise. After keeping the temperature for 1 hour,diethyl-ether solution (5 ml) of dichlorophenyl phosphine (0.22 g, 1.22mmol) was added dropwise. After having temperature raised to a roomtemperature and stirring for 15 hours, it was cooled at 0° C. and 5%NaHCO₃ aqueous solution was added dropwise. The aqueous phase wasextracted with toluene, the organic layer was collected, and washed withwater and then saturated NaCl aqueous solution. The solvent wasdistilled off and 1.11 g of crude product was obtained. By purificationusing Silica gel column chromatography (eluent hexane:ethylacetate=100:1(0.1% triethylamine)), and Compound A was obtained in 0.52 g (purity96.1% and yield 68.5%).

¹H-NMR (CDCl₃, 300 MHZ)

δ7.77 (d, 2H), 7.31-7.13 (m, 7H), 4.198t, 4H), 1.96-1.87 (m, 4H),1.69-1.52 (m, 4H), and 1.35-1.26 (m, 16H) and 0.90 (t, 6H)

Synthetic Example 5 Synthesis of Compound B

The above 4,4′-dibromo-2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl 5.00 g(apparent mole number 6.1 mmols) was put in a 300 ml three-necked flaskwhich was flame dried and argon gas substituted, and dissolved indehydrated diethyl ether 50 ml. This solution was cooled to −90° C. bymethanol/liquid nitrogen, and n-BuLi 8.4 ml (1.6M n-hexane solution,13.4 mmol) was added dropwise. After keeping the temperature for 1 hour,sulfur 0.20 g (6.1 mmol) was added. After having the temperature raisedto a room temperature, and stirring for 3.5 hours, sulfur 2.00 g (61mmol) was added and stirred further 4 hours. Then, it was cooled at 0°C. and 15 ml of 1N hydrochloric acid was added dropwise. The aqueousphase was extracted with diethylehter, the organic layer was collected,and washed with water and then saturated NaCl aqueous solution. Afterbeing dried with sodium sulfate, the solvent was distilled off and 6.26g of crude product was obtained. By purification using Silica gel columnchromatography (eluent hexane:ethylacetate=20:1), and Compound B wasobtained in 0.91 g (p. 87.3%, y.20.7%).

¹H-NMR (CDCl₃, 300 MHz)

δ7.69 (s, 2H), 7.08 (s, 2H), 4.09 (t, 4H), 1.92-1.81 (m, 4H), 1.58-1.26(m, 20H), 0.88 (t, 6H)

Synthetic Example 6 Synthesis of Compound C

The above 4,4′-dibromo-2,2′-di-iodo-5,5′-dioctyloxy-1,1′-biphenyl 5.0 gwas charged into a 100 ml flask under nitrogen atmosphere, andtetrahydrofuran 50 ml was added to dissolve it. It was cooled at 90° C.and 8.4 ml of N-Butyl Lithium/1.6M-hexane solution was added dropwise.After 1.5 hours stirring, tetrahydrofuran solution 61 g ofmagnesium-bromide 3.38 g was added, and raised the temperature to a roomtemperature, and further stirred for 1.5 hours. It was cooled to −90° C.again, and 1,2-dichlorotetramethyl disilane 1.60 g was added. Then thetemperature was raised and reacted for 8.5 hours with refluxing.

After having distilled off the solvent, toluene 100 ml was charged andstirred, and then insoluble matters were filtrated. The solvent wasdistilled off again and a crude product was obtained. The crude productwas purified by silica gel chromatography (eluent hexane:triethylaminetoluene=800:5), and 0.24 g of Compound C was obtained.

¹H-NMR (300 MHz/CDCl₃):

δ (ppm)=0.20 [s, 12H], 0.89 [t, 6H], 1.1˜1.6 [m, 20H], 1.89 [m, 4H],4.08 [t, 4H], 6.92 [s, 2H], 7.57 [s, 2H]

Synthetic Example 7 Synthesis of Compound D

In an inert atmosphere, 3-bromophenol 90 g was dissolved in ethanol 600ml. 39 g of potassium hydroxide was added further, and dissolved at 70°C. 1-bromo-3,7-dimethyloctane 126 g was added dropwise from a droppingfunnel for 15 minutes. After the dropwise adding, the temperature wasraised to 84° C., and stirring with heating was carried out for about 22hours.

After the heating, it was standing to cool to a room temperature. Thereaction liquid was divided into two portions, each of which was addedinto 500 ml of water, and ethanol was distilled off with usingevaporator. After distilling off the ethanol, the residual solutionswere collected together and into three portions. To each of theportions, 300 ml of ethyl acetate was added and partitioned,respectively, and the organic layer was washed with 200 ml of watertwice. After having collected the organic layers and distilling off thesolvent using an evaporator, drying was carried out at 90° C. for 5hours under reduced pressure using a rotary pump. About 150 g of3-(3,7-dimethyloctyloxy)-bromobenzene was obtained as an oily product.Dried tetrahydrofuran 100 ml, magnesium 7.5 g and small quantity ofiodine were charged into a three-necked flask under an inert atmosphere.Using a dropping funnel, the above 3-(3,7-dimethyloctyloxy)-bromobenzene 90 g was added dropwise for 50 minutes. After the dropwiseadding, dried tetrahydrofuran 200 ml was added and heat-stirring wascarried out for 2 hours with refluxing to prepare a Grignard reagent.After the heating, it was left standing to cool to a room temperature.Trimethyl borate 38 g and dried tetrahydrofuran 300 ml were charged intoanother three-necked flask, and the flask was cooled by a dryice-acetone bath. Using a dropping funnel, the above Grignard reagentsolution was added dropwise for 35 minutes. After the dropwise addingthe reaction liquid was heated to a room temperature. After having addedthe reaction liquid to a dilute sulfuric acid (sulfuric acid 12 ml/water360 ml) and stirring, it was divided into two portions, and each of themwas extracted with 150 ml and 100 ml of ethyl acetate. The organiclayers were collected together and divided into three portions, and eachof them was washed with 100 ml of water. The organic layers afterwashing were collected together and the solvent was distilled off usingan evaporator. A suspension of the solid content was produced by adding100 ml of hexane and filtrated. Further, it washed with 100 ml ofhexane. White solid of 3-(3,7-dimethyloctyloxy)-phenyl boric acid 63 gwas obtained. Under an inert atmosphere, to a three-necked flask, theabove 3-(3,7-dimethyloctyloxy)-bromobenzene 60 g, toluene 250 ml, water250 ml, potassium carbonate 62 g and tetrakis(triphenylphosphine)palladium complex 1.2 g were charged. After bubblingof the solution with argon for 20 minutes to deaerate oxygen, the above3-(3,7-dimethyloctyloxy)-phenyl boric acid 63 g was added, thetemperature was raised to 90° C., and stirring with heating was carriedout for 8 hours. After the heating, it was left to stand for cooling toa room temperature. After partitioning the toluene layer, coloringcomponents were removed with silica gel chromatography. The solvent wasdistilled off and 98 g of Compound D was obtained as an oily product.

¹H-NMR (200 MHz/CDCl₃):

ä(ppm)=0.87 [d, 12H], 0.94 [d, 6H], 1.1˜1.8 [m, 20H], 4.0 4 [t, 4H],6.88 [d, 2H], 7.1˜7.3 [m, 4H], 7.32 [t, 2H]

Synthetic Example 8 Synthesis of Compound E

The above compound D 20 g was dissolved in dried N,N-dimethylformamide400 ml. A solution of N-bromosuccinimide 15.5 g/N,N-dimethylformamide300 ml was added dropwise for 90 minutes with ice cooling. After thedropwise adding, the ice bath was removed and stirred overnight. Afterdistilling off the solvent, it was dissolved in toluene 200 ml, andwashed with 200 ml of water 3 times, and the solvent was distilled off.26 g of oily product was obtained. From the measurement result of aLC-MS spectrum, isomers having different bromo substituted positionswere observed, and the purity of Compound E was about 65% (LC areapercentage).

¹H-NMR (200 MHz/CDCl₃):

ä(ppm)=0.86-[d, 12H], 0.93-[d, 6H], 1.1˜1.8 [m, 20H], 3.97-[t, 4H], 6.79[d, 2H], 6.82 [d, 2H], 7.52-[d, 2H]

MS (APCI (+)):M⁺ 624

Synthetic Example 9 Synthesis of Compound F

In a 200 ml four-necked flask whose inside atmosphere was replaced withargon, Compound E 5.00 g (8.0 mmol) was dissolved in 80 ml dehydratedether, and cooled to −78° C. To this solution, n-butyllithium 11 ml(17.6 mmol, 1.6M hexane solution) was added dropwise, and stirred for3.5 hours. This solution was added dropwise to an ether solution 500 mlof tetrachlorosilane 25.8 g (152 mmol) cooled at −78° C. After stirringfor 1 hour, the temperature was raised to a room temperature, and it wasstirred for 15 hours. The reaction liquid was filtered under argonatmosphere, and the filtrate was condensed to give a crude product 4.52g. The resultant crude product was put into a 500 ml three-necked flaskwhose inside was replaced with argon gas, and dissolved in 90 mldehydrated ether, and cooled to −78° C. Phenyl lithium 23 ml (24 mmol,1.06M cyclopentane/ether solution) was added dropwise to this solution.After stirring for 20 minutes, it was raised to a room temperature andstirred for 4 hours. Water was added and partitioned and the aqueouslayer was extracted with diethyl ether. The organic layers werecollected together and washed with saturated sodium hydrogencarbonateaqueous solution and saturated NaCl aqueous solution. After drying withsodium hydrogensulfate, the solvent was distilled off, and 6.66 g of acrude product of Compound F was obtained.

ä 0.86 (d, 12H), 0.97 (d, 6H), 1.16-1.90 (m, 20H), 4.09 (br, 4H),6.84-6.88 (m, 2H), 7.29-7.66 (m, 28H)

MS (APCI(+)):M⁺ 647.4

Synthetic Example 10 Synthesis of Compound G

In a 300 ml three-necked flask whose inside atmosphere was replaced withargon, Compound F 5.00 g (purity 85.1%, 6.6 mmol) was put in anddissolved in dehydrated DMF65 ml. N-bromosuccinimide 2.45 g (13.8 mmol)was charged to this solution. After stirring at a room temperature for 5hours, it was extracted with hexane (80 ml×5) in a glove box. Thesolvent was distilled off, and 14.02 g of a crude product (LC areapercentage 19.9% including DMF) was obtained. After separation withreversed-phase silica gel column chromatography(acetonitrile:toluene=20:1), fractions were extracted with hexane (inorder to remove a minute amount of acetic acid in acetonitrile), andwashed by 5% sodium-hydrogencarbonate aqueous solution and satu-ratedNaCl aqueous solution. After drying with sodium sulfate, the solvent wasdistilled off, and 0.30 g (LC area percentage 58%, yield 3.3%) ofCompound G was obtained.

¹H-NMR (300 MHz/acetone-d₆): δ 0.86 (d, 12H), 0.99 (d, 6H), 1.17-1.95(m, 20H), 4.31 (br, 4H), 7.37-7.50 (m, 2H), 7.68-7.71 (m, 28H), 7.81 (s,2H), 8.00 (s, 2H)

MS (APCI(+)):M⁺ 804.9

Synthetic Example 11 Synthesis of Compound H

Compound F 3.91 g (purity 85.1%, 5.1 mmol) was put in a 200 ml threenecked flask whose inside was replaced with argon gas, and dissolved indehydrated DMF 50 ml. NCS 1.47 g (10.8 mmol) was charged into thissolution. NCS was added, with pursuing the reaction by LC. (total 2.62g). After stirring for 60 hours at a room temperature, it was extractedwith hexane (100 ml×5) in a glove box. The solvent was distilled off,and 12.73 g (LC area percentage 34.1%, including DMF) of a crude productwas obtained. After separation with reversed-phase silica gel columnchromatography (acetonitrile:toluene=20:1), the fractions were extractedwith hexane, and washed with 5% sodium-hydrogencarbonate aqueoussolution and saturated NaCl aqueous solution (in order to remove theminute amount of acetic acid in acetonitrile). After drying with sodiumsulfate, the solvent was distilled off, and 0.18 g (82.5% of LC areapercentage, 3.6% of yield) Compound H was obtained.

¹H-NMR (300 MHz/acetone-d₆):

δ 0.87 (d, 12H), 0.99 (d, 6H), 1.10˜1.94 (m, 20H), 4.28 (b r, 4H),7.30˜7.71 (m, 10H), 7.83 (br, 4H)

MS (APCI(+)):M⁺ 715.3

Example 1 Condensation Polymerization of Compound A

<Synthesis of Polymer 1>

Compound A 0.59 g, N,N′-bis(4-bromophenyl)-N,N′-bis(4-n-butylphenyl)-1,4-phenylenediamine 0.26 g,2,2′-bipyridyl 0.48 g were chargedinto a reaction vessel, and the atmosphere of the reaction system wasreplaced with nitrogen gas. To this, 35 ml of tetrahydrofuran(dehydrated solvent) which was deaerated beforehand by bubbling withargon gas was added. Next, bis(1,5-cyclo octadiene) nickel (O) 0.85 gwas added to this mixed solution, and reacted at 60° C. for 3 hours. Thereaction was performed in nitrogen-gas atmosphere. After the reaction,this solution was cooled and then poured into a mixed solution of 25%aqueous-ammonia 10 ml/methanol 120 ml/ion-exchanged water 50 ml, andstirred for about 1 hour. Next, resulting precipitate was collected byfiltration. The precipitate was washed with ethanol, and dried at areduced pressure for 2 hours. Next, this precipitate was dissolved intoluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL, it wasstirred for 1 hour. The aqueous layer was removed, and 4%aqueous-ammonia 30 mL was added to an organic layer, and after stirringfor 1 hour, the aqueous layer was removed. The organic layer was addeddropwise to methanol 200 mL, and stirred for 1 hour. The depositedprecipitate was filtered and dried for 2 hours at a reduced pressure,and then dissolved in toluene 30 mL. Then, it was purified by passingthrough alumina column (20 g of alumina). The collected toluene solutionwas added dropwise to methanol 250 mL, stirred for 1 hour, and depositedprecipitate was filtered and dried for 2 hours at a reduced pressure.The yield of the resulting polymer was 0.06 g. This polymer is referredto as Polymer 1.

The polystyrene reduced number average molecular weight of Polymer 1 was5.0×10², and the polystyrene reduced weight average molecular weight was6.2×10³.

Example 2 Condensation Polymerization of Compound B

<Synthesis of Polymer 2>

Compound B 0.35 g, N,N′-bis(4-bromophenyl)-N,N′-bis(4-n-butylphenyl)-1,4-phenylenediamine 0.16 g, 2,2′-bipyridyl 0.37 g were chargedinto a reaction vessel, and the atmosphere of the reaction system wasreplaced with nitrogen gas. To this, 28 ml of tetrahydrofuran(dehydrated solvent) which was deaerated beforehand by bubbling withargon gas was added. Next, bis(1,5-cyclo octadiene) nickel (0) 0.70 gwas added to this mixed solution, and reacted at 60° C. for 3 hours. Thereaction was performed in nitrogen-gas atmosphere. After the reaction,this solution was cooled and then poured into a mixed solution of 25%aqueous-ammonia 10 ml/methanol 120 ml/ion-exchanged water 50 ml, andstirred for about 1 hour. Next, resulting precipitate was collected byfiltration. The precipitate was washed with ethanol, and dried at areduced pressure for 2 hours. Next, this precipitate was dissolved intoluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL, it wasstirred for 1 hour. The aqueous layer was removed, and 4%aqueous-ammonia 30 mL was added to an organic layer, and after stirringfor 1 hour, the aqueous layer was removed. The organic layer was addeddropwise to methanol 200 mL, and stirred for 1 hour. The depositedprecipitate was filtered and dried for 2 hours at a reduced pressure,and then dissolved in toluene 30 mL. Then, it was purified by passingthrough alumina column (20 g of alumina). The collected toluene solutionwas added dropwise to methanol 250 mL, stirred for 1 hour, and depositedprecipitate was filtered and dried for 2 hours at a reduced pressure.The yield of the resulting polymer was 0.13 g. This polymer is referredto as Polymer 2.

The polystyrene reduced number average molecular weight of Polymer 2 was6.2×10³, and the polystyrene reduced weight average molecular weight was5.1×10⁴.

Example 3 Condensation Polymerization of Compound C)<

<Synthesis of Polymer 3>

Compound C 0.30 g, N,N′-bis(4-bromophenyl)-N,N′-bis(4-n-butylphenyl)-1,4-phenylenediamine 0.13 g, 2,2′-bipyridyl 0.30 g were chargedinto a reaction vessel, and the atmosphere of the reaction system wasreplaced with nitrogen gas. To this, 20 ml of tetrahydrofuran(dehydrated solvent) which was deaerated beforehand by bubbling withargon gas was added. Next, bis(1,5-cyclo octadiene) nickel (O) 0.52 gwas added to this mixed solution, and reacted at 60° C. for 3 hours. Thereaction was performed in nitrogen-gas atmosphere. After the reaction,this solution was cooled and then poured into a mixed solution of 25%aqueous-ammonia 10 ml/methanol 120 ml/ion-exchanged water 50 ml, andstirred for about 1 hour. Next, resulting precipitate was collected byfiltration. The precipitate was washed with ethanol, and dried at areduced pressure for 2 hours. Next, this precipitate was dissolved intoluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL, it wasstirred for 1 hour. The aqueous layer was removed, and 4%aqueous-ammonia 30 mL was added turn organic layer, and after stirringfor 1 hour, the aqueous layer was removed. The organic layer was addeddropwise to methanol 200 mL, and stirred for 1 hour. The depositedprecipitate was filtered and dried for 2 hours at a reduced pressure,and then dissolved in toluene 30 mL. Then, it was purified by passingthrough alumina column (20 g of alumina). The collected toluene solutionwas added dropwise to methanol 250 mL, stirred for 1 hour, and depositedprecipitate was filtered and dried for 2 hours at a reduced pressure.The yield of the resulting polymer was 0.11 g. This polymer is referredto as Polymer 3.

The polystyrene reduced number average molecular weight of Polymer 3 was1.4×10³, and the polystyrene reduced weight average molecular weight was4.9×10⁴.

Example 4 Condensation Polymerization of Compound G

<Synthesis of Polymer 4>

Compound G 0.20 g, N,N′-bis(4-bromophenyl)-N,N′-bis(4-n-butylphenyl)-1,4-phenylenediamine 0.07, 2,2′-bipyridyl 0.17 g were chargedinto a reaction vessel, and the atmosphere of the reaction system wasreplaced with nitrogen gas. To this, 20 ml of tetrahydrofuran(dehydrated solvent) which was deaerated beforehand by bubbling withargon gas was added. Next, bis(1,5-cyclo octadiene) nickel (0) 0.3 g wasadded to this mixed solution, and stirred at a room temperature for 10minutes, and reacted at 60° C. for 3 hours. The reaction was performedin nitrogen-gas atmosphere. After the reaction, this solution was cooledand then poured into a mixed solution of methanol 120 ml/ion-exchangedwater 200 ml, and stirred for about 1 hour. Next, resulting precipitatewas collected by filtration. The precipitate was dried and dissolved inchloroform. The solution was filtered to remove insoluble matters, andthe chloroform was distilled off to give a solid product. This solidproduct was washed with methanol and dried at a reduced pressure toyield a polymer 0.08 g. This polymer is referred to as Polymer 4.

The polystyrene reduced number average molecular weight of Polymer 4 was1.5×10³, and the polystyrene reduced weight average molecular weight was5.0×10³.

Example 5 Polymerization of Compound H

<Synthesis of Polymer 5>

Compound H 0.21 g, N,N′-bis(4-bromophenyl)-N,N′-bis(4-n-butylphenyl)-1,4-phenylenediamine 0.10, 2,2′-bipyridyl 0.27 g were chargedinto a reaction vessel, and the atmosphere of the reaction system wasreplaced with nitrogen gas. To this, 20 ml of tetrahydrofuran(dehydrated solvent) which was deaerated beforehand by bubbling withargon gas was added. Next, bis(1,5-cyclo octadiene) nickel (O) 0.5 g wasadded to this mixed solution, and stirred at a room temperature for 10minutes, and reacted at 60° C. for 3 hours. The reaction was performedin nitrogen-gas atmosphere. After the reaction, this solution was cooledand then poured into a mixed solution of methanol 100 ml/ion-exchangedwater 200 ml, and stirred for about 1 hour. Next, resulting precipitatewas collected by filtration. The precipitate was dried and dissolved intoluene. The solution was filtered to remove insoluble matters, and thetoluene was distilled off to give a solid product. This solid productwas washed with ethanol and dried at a reduced pressure to yield apolymer 0.09 g. This polymer is referred to as Polymer 5.

The polystyrene reduced number average molecular weight of Polymer 5 was1.6×10³, and the polystyrene reduced weight average molecular weight was5.4×10³.

Example 6 Fluorescence Characteristics

Each of the 2 wt % chloroform solutions of Polymers 1 to 5 were spincoated respectively on quartz, and thin films of polymeric fluorescentsubstance were produced. The fluorescence spectrum of these thin filmswere measured using a spectrophotometer (Hitachi 850). All of them havestrong fluorescence and they respectively showed fluorescence peakwavelengthes shown in Table 1. TABLE 1 Fluorescence peak wavelengthPolymer (nm) Polymer 1 516 Polymer 2 468 Polymer 3 458 Polymer 4 466Polymer 5 458

Calculation Examples

Calculation examples of bond-distance ratio are shown b elow. Thecalculation was performed using Gaussian 98 (b31yp/6-31 g*).

Calculation Example 1 Comparison of a Monomer with a Trimer

The bond-distance ratio of a monomer having hydrogen atoms at thebonding positions in polymerization was compared with that of thetrimer.

Calculation compound Bond-distance ratio Calculation compound 1 1.254Calculation compound 2 (Center) 1.256 Calculation compound 2 (Terminal)1.254

The difference of the bond-distance ratios was small, and thebond-distance ratio of a polymer can be approximated by that of themonomer having hydrogen atoms at the bonding position in polymerization.

Calculation Example 2 Comparison of the Side Chains

The bond-distance ratios were compared between a compound having methoxygroup as the alkyloxy group side chain and a compound having n-octyloxygroup.

Calculation compound Bond-distance ratio Calculation compound 3 1.254Calculation compound 4 1.254

The difference of the bond-distance ratios was small, and thebond-distance ratio of a compound having n-octyloxy group can beapproximated by that of the compound having methoxy group.

Calculation Example 3 Calculation of the Compounds Produced in Examples

In the formula, Ph represents a phenyl group. Calculation compoundBond-distance ratio Calculation compound 5 1.329 Calculation compound 61.304 Calculation compound 7 1.338 Calculation compound 8 1.268Comparative Example 1 1.085 Comparative Example 2 1.071

The polymer of the present invention is a new polymer which can be usedas a light-emitting material, a charge transporting material, etc.

1. A polymer having a polystyrene reduced number average molecularweights of 10³-10⁸, and comprising a repeating unit represented byformula (I),

wherein, R¹, R², R³, R⁴, R⁵, and R⁶, each independently represent ahydrogen atom, a halogen atom, an alkyl group, alkynyl group, alkynylgroup, alkyloxy group, alkylthio group, an alkylamino group, aryl group,aryloxy group, arylthio group, arylemino group, arylalkyl group.arylalkyloxy group, aryl alkylthio group, arylalkylamino group,substituted silyl group, aryl group, aryloxy group, imino group, amidegroup, arylalkenyl group, arylalkynyl group, monovalent heterocyclicgroup, or cyano group; R² and R³ may be connected to form a ring; R⁴ andR⁵ may be connected to form a ring; A¹ is a divalent group representedby formula (6),

wherein, A² represents Si; R⁸ and R⁹ each independently represent analkyl group, alkyloxy group, alkylthio group, alkylamino group, arylgroup, aryloxy group, arylthio group, arylamino group, arylalkyl group,arylalkyloxy group, arylalkylthio group, arylalkylamino group, acyloxygroup, amide group, or monovalent heterocyclic group; and l represents1; and the polymer further comprises a repeating unit represented byformula (7) or formula (8),—Ar⁶—(CR¹⁷═CR¹⁸)n—  (7) wherein, Ar⁶ represents an arylene group or adivalent heterocyclic group; R¹⁷ and R¹⁸ each independently represent ahydrogen atom, an alkyl group, aryl group, monovalent heterocyclicgroup, or cyano group; and n represents 0 or 1,

wherein, Ar¹ and Ar² each independently represent an arylene group or adivalent heterocyclic group; R¹¹ represents a group represented by analkyl group, aryl group, monovalent heterocyclic group, and a grouprepresented by the below formula (9) or (10); and m represents aninteger of 1-4,

wherein, Ar³ represents an arylene group or a divalent heterocyclicgroup; R¹² represents a hydrogen atom, an alkyl group, aryl group,monovalent heterocyclic group, or a group represented by the belowformula (10); Y¹ represents —CR¹³═CR⁴— or —C≡C—; R¹³ and R¹⁴ eachindependently represent a hydrogen atom, an alkyl group, aryl group,monovalent heterocyclic group, or cyano group; and p represents aninteger of 0-2,

wherein, Ar⁴ and Ar⁵ each independently represents an arylene group or adivalent heterocyclic group; R¹⁵ represents an alkyl group, aryl group,or monovalent heterocyclic group; R¹⁶ represents a hydrogen atom, analkyl group, aryl group, or monovalent heterocyclic group; and qrepresents an integer of 1-4.
 2. A polymer according to claim 1, whereinR² and R⁵ each independently represent an alkyloxy group, alkylthiogroup, alkylamino group, aryloxy group, arylthio group, arylamino group,arylalkyloxy group, arylalkylthio group, or arylalkylamino group.
 3. Apolymer according to claim 2, wherein R² and R⁵ each independentlyrepresent alkyloxy group, aryloxy group, or arylalkyloxy group.
 4. Aprocess for producing a polymer according to claim 1, wherein acondensation polymerization is carried out using a compound representedby the below formula (II),

wherein, R¹, R², R³, R⁴, R⁵, R⁶, and A¹ respectively represent the samegroups as those in formula (I) of claim 1; x¹ and x² each independentlyrepresent a substituent capable of condensation polymerization.
 5. Acompound represented by formula (II),

wherein, R¹, R², R³, R⁴, R⁵, and R⁶ each independently represent ahydrogen atom, a halogen atom, an alkyl group, alkenyl group, alkynylgroup, alkyloxy group, alkylthio group, an alkylamino group, aryl group,aryloxy group, arylthio group, arylamino group, arylalkyl group,arylalkyloxy group, aryl alkylthio group, arylalkylamino group,substituted silyl group, acyl group, acyloxy group, imino group, amidegroup, arylalkenyl group, arylalkynyl group, monovalent heterocyclicgroup, or cyano group; R² and R³ may be connected to form a ring; R⁴ andR⁵ may be connected to form a ring; A¹ is a divalent group representedby formula (6),

wherein, A² represents Si; R⁸ and R⁹ each independently represent analkyl group, alkyloxy group, alkylthio group, alkylamino group, arylgroup, aryloxy group, arylthio group, arylamino group, arylalkyl group,arylalkyloxy group, arylalkylthio group, arylalkylamino group, acyloxygroup, amide group, or monovalent heterocyclic group; l represents 1;and x¹ and x² each independently represent a substituent capable ofcondensation polymerization.
 6. A compound according to claim 5, whereinR² and R⁵ each independently represent an alkyloxy group, alkylthiogroup, alkylamino group, aryloxy group, arylthio group, arylamino group,arylalkyloxy group, arylalkylthio group, or arylalkylamino group.
 7. Acompound according to claim 6, wherein R² and R⁵ each independentlyrepresent an alkyloxy group, aryloxy group, or arylalkyloxy group.
 8. Acompound according to claim 5, wherein X¹ and X² each independentlyrepresent a halogen atom, alkyl sulfonate group, aryl sulfonate group,or arylalkyl sulfonate group.
 9. A compound according to claim 5,wherein X¹ and X² each independently represent a halogen atom.
 10. Aprocess for producing a polymer according to claim 4, wherein X¹ and X²each independently represent a halogen atom, alkyl sulfonate group, arylsulfonate group or arylalkyl sulfonate group and wherein thecondensation polymerization is carried out using a palladium catalyst ora nickel catalyst.
 11. A process for producing a compound according toclaim 5, wherein the compound represented by the below formula (19) isreacted with a halogenation reagent,

wherein, R¹, R², R³, R⁴, R⁵, and R⁶ each independently represent ahydrogen atom, a halogen atom, an alkyl group, alkenyl group, alkynylgroup, alkyloxy group, alkylthio group, an alkylamino group, aryl group,aryloxy group, arylthio group, arylamino group, arylalkyl group,arylalkyloxy group, aryl alkylthio group, arylalkylamino group,substituted silyl group, acyl group, acyloxy group, imino group, amidegroup, arylalkenyl group, arylalkynyl group, monovalent heterocyclicgroup, or cyano group; R² and R³ may be connected to form a ring; and R⁴and R⁵ may be connected to form a ring; R⁸, and R⁹ each independentlyrepresent an alkyl group, alkyloxy group, alkylthio group, alkylamiuogroup, aryl group, aryloxy group, arylthio group, arylamino group,arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkylaminogroup, acyloxy group, amide group, or monovalent heterocyclic group; andl represents 1 or
 2. 12. A process for producing a dibenzosilolederivative according to claim 11, wherein N—halogenocompound is used asthe halogenation reagent.
 13. A dibenzosilole derivative represented byformula (19) as claimed in claim
 11. 14. A dibenzosilole derivativeaccording to claim 13, wherein all of R¹, R³, R⁴, and R⁶ in the aboveformula (19) are hydrogen atoms.
 15. A polymer electronic deviceincluding a polymer according to claim
 1. 16. A polymeric fluorescentsubstance consisting of a polymer according to claim
 1. 17. A polymerlight-emitting device having a light emitting layer between theelectrodes consisting of an anode and a cathode, wherein saidlight-emitting layer contains the polymer according to claim
 1. 18. Aflat light source comprising a polymer light-emitting device accordingto claim
 17. 19. A segment display apparatus comprising a polymerlight-emitting device according to claim
 17. 20. A dot-matrix displayapparatus comprising a polymer light-emitting device according to claim17.
 21. A liquid crystal display comprising a polymer light-emittingdevice according to claim 17 as a back light.